多孔聚离子液体的合成与应用

聚离子液体(Poly(ionic liquid)s,PIL)是分子结构中含有离子液体结构单元的一类离子聚合物,兼具离子液体小分子的离子电导性和聚合物可加工性能。多孔聚离子液体材料(Porous PILs),结合了多孔材料大比表面积和聚离子液体的导电性及离子交换等特性,在功能高分子材料、电化学响应材料以及能源科学等领域表现出广泛的应用前景。本文综述了多孔聚离子液体的分子设计与合成方法,及其在智能响应材料、水处理、高效催化、多孔碳材料、生物医用材料等领域的潜在应用。     

功能离子液体/氧化硅基多孔复合材料*

利用有巨大界面特征和发达孔道结构的氧化硅基多孔材料作为功能离子液体的载体,不仅可实现离子液体的固相化从而解决均相离子液体分离难的瓶颈,而且也可增加离子液体的比表面积进而提高离子液体的使用效率和稳定性;探索结合离子液体和氧化硅基多孔材料双重优点的目标功能材料的制备及应用成为近年来的一个研究热点。本文综述了离子液体/氧化硅基多孔复合材料的最新研究进展,探讨了其合成手段的有效性,并对其应用前景进行了展望。     

氮掺杂多孔炭材料的制备及在多相催化中的应用

氮掺杂多孔炭材料,不仅具有多孔炭材料的较高的比表面积、丰富的孔结构、良好的稳定性及耐高温耐酸碱性等优点,同时氮原子的引入使材料表现出优异的导电性能及电子传输能力,使得炭材料具有了一定的碱性及催化性能,是目前多相催化及材料领域的一个研究热点。本文综述了氮掺杂多孔炭的制备方法及在多相催化中的应用,并指出了该领域未来研发的重点及应用前景。     

多孔氧化物块体材料的制备及其对重金属离子吸附研究进展

目前去除重金属离子的方法较多,其中吸附法因操作简单、经济性好而被广泛使用。多孔氧化物块体材料作为新兴的吸附材料具有比表面积高、机械强度高及可回收性好等特点,但吸附选择性差以及孔结构单一的缺陷限制了其在水体重金属处理中的应用。本文详细叙述了多孔氧化物块体材料的多种制备方法,并分别讨论了各方法的优势及其不足。介绍了近几年研究较多的多孔氧化物块体材料及其制备方法与特性。最后,对多孔氧化物块体材料对 Pb、Cd及 Cr等重金属离子吸附性能的影响因素及改善措施方面进行了总结分析,并指出多种材料的复合、材料表面的接枝改性及分级多孔结构的构建会增强对重金属离子的吸附性能。期望本文为多孔氧化物块体材料的制备及其在重金属离子吸附方面的应用提供参考。     

离子液体中制备无机材料

离子液体作为潜在的“绿色”溶剂,具有许多传统溶剂无法比拟的优异性能,在有机合成、催化、液液分离和萃取等领域引起了广泛的研究。而在离子液体领域无机材料的制备是一个较新的发展分支,现已利用其合成出多种具有独特结构和性能的无机材料。本文就离子液体在无机材料制备方面的应用及发展趋势进行了综述。目前,对于制备无机材料,离子液体主要是作为电解液、表面活性剂或溶剂,本文介绍了其在应用中的优缺点,并指出该领域未来的发展趋势是离子热合成和集模板-溶剂-反应物于一身的离子液体反应。     

基于离子液体修饰的金属有机骨架材料在CO_2分离与转化方面的研究进展

基于离子液体修饰的金属有机骨架材料(IL@MOF)兼具离子液体和金属有机骨架材料的优势,具有吸附效果好、易分离且可重复利用等特点,在CO_2气体分离与转化领域展示出了良好的应用潜力。本文综述了离子液体修饰金属有机骨架材料的制备方法及其在CO_2分离与转化领域的最新应用研究,并对其未来发展趋势进行了展望。     

离子液体萃淋树脂及其在稀土分离和纯化中的应用

总结了作者及其团队近10年来在离子液体萃淋树脂的制备方法及其在稀土分离中的应用研究进展。离子液体萃淋树脂是一种新型的高效固体分离材料,其制备方法有物理负载法、化学负载法、溶解凝胶法和膜负载法等,所用载体一般为高比表面多孔的高分子树脂、SiO_2等。离子液体萃淋树脂具有离子液体的可设计性,可根据不同的结构需求设计合成出不同性能的离子液体萃淋树脂,同时可以减少萃取剂的流失,适用于高效和高选择性的分离和纯化稀土离子,是溶剂萃取法萃取分离稀土的有效补充和完善。     

空腔型纳米炭的制备与应用

空腔型纳米炭具有低密度、高表面积/体积比、较大的内部空间及可调的炭壳厚度和孔隙结构等特性,在新材料和新能源等相关领域展现出巨大的应用潜力,成为目前多孔炭材料研究的重要分支.本文讨论了空腔型纳米炭的制备方法及其形貌结构的调控思路,分析了不同方法的优缺点;综合评述了其在能源存储、催化转化、吸附分离和生物医药领域的应用进展,并对现存问题及发展趋势进行了总结与展望.     

新型高分子基多孔炭材料的设计制备与功能化策略

多孔炭材料具有孔隙率丰富、导电率高、结构稳定以及物理化学性质可调等优点,广泛应用于能源储存与转换、吸附分离、催化、石油化工和生物医药等领域.原料结构是影响多孔炭材料结构和性能的关键因素.高分子理化结构丰富可调,且具有良好的成炭性和形貌继承性,是制备高性能多孔炭材料的理想原料.本专论结合近期国内外研究进展以及我们课题组相关工作,系统总结了高分子衍生多孔炭材料的直接炭化法和模板法设计制备理论,讨论了炭骨架功能化策略,归纳了高分子的化学结构及微观形貌对多孔炭材料的孔道与骨架结构的影响规律,并展望了这一领域未来的研究方向.     

离子液体中的纤维素溶解、再生及材料制备研究进展

近年来,离子液体作为一类新型的环境友好介质和软功能材料受到了广泛的关注,并被广泛应用于有机合成、催化、电化学、分离分析等领域.其中,离子液体中的纤维素化学是当前离子液体研究的热点领域之一,离子液体的出现也为纤维素化学的进一步发展提供了广阔的空间.离子液体以其低熔点、高稳定性、低蒸汽压、溶解性能可调节等优异的理化性能已被证实为纤维素的有效溶剂,被广泛用于纤维素的溶解、再生及应用研究.综述了离子液体中纤维素的溶解行为,包括纤维素溶解度的影响因素、纤维素在离子液体中的溶解过程、纤维素的溶解及再生机理等,以及离子液体中基于纤维素的新型材料制备研究进展,并对离子液体中纤维素研究存在的问题和未来的发展方向进行了总结和展望.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.